Accepted Manuscript

Electrochemical performances of silver nanoparticles decorated polyaniline/graphene

nanocomposite in different electrolytes

Saptarshi Dhibar, Chapal Kumar Das

PII: S0925-8388(15)30854-9
DOI: 10.1016/j.jallcom.2015.08.158
Reference: JALCOM 35153

To appear in: Journal of Alloys and Compounds

Received Date: 2 June 2015

Revised Date: 18 August 2015
Accepted Date: 19 August 2015

Please cite this article as: S. Dhibar, C.K. Das, Electrochemical performances of silver nanoparticles
decorated polyaniline/graphene nanocomposite in different electrolytes, Journal of Alloys and
Compounds (2015), doi: 10.1016/j.jallcom.2015.08.158.

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 ACCEPTED MANUSCRIPT

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Electrochemical performances of silver nanoparticles decorated

polyaniline/graphene nanocomposite in different electrolytes

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Saptarshi Dhibar and Chapal Kumar Das*

Materials Science Centre, Indian Institute of Technology Kharagpur, Kharagpur – 721302, India

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*To whom all the correspondences should be addressed.

Chapal Kumar Das (Email: chapal12@yahoo.co.in)

Tel.: +91-3222-283978

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Abstract

In the present study, a simple, inexpensive and novel synthetic procedure was used for

the preparation of Silver-Polyaniline/Graphene [Ag-PANI/Gr] nanocomposite as superior

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supercapacitor electrode material. The probable interaction of Ag with PANI and Gr were

characterized by Fourier transform infrared, UV-visible, and Raman spectroscopies. The

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formation of Ag nanoparticles in the PANI coated Gr sheets were confirmed by morphological

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study. The maximum specific capacitance of 591 F/g has been achieved for the nanocomposite at

5 mV/s scan rate in 1 M KCl electrolyte. The nanocomposite also attained superior energy as

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well as power density. Here, both Ag nanoparticles and Gr take part for the increment of specific
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capacitance of the nanocomposite. The nanocomposite showed enhanced electrical conductivity

of 5.17 S/cm and also reached nonlinear current-voltage characteristics. The higher thermal
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stability also observed for the nanocomposite. Depending on those superior properties the Ag-

PANI/Gr nanocomposite can be used for supercapacitor electrode material.

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Keywords- Graphene; Silver nanoparticles; Polyaniline; Supercapacitors

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1. Introduction

The world is now facing a serious energy problem described by growing energy costs and

reducing production capacities for oil and gas. Significant efforts have been committed to the

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expansion of alternative energy storage/conversion devises in response to supply depletion. In

the past few years, research into supercapacitors has experienced an enormous growth due to

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their high specific capacitance, pulse power capabilities, long cycle life, fast charge and

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discharge rates, low internal resistance, high power densities, and sustainable features [1-6]. Due

to these special properties supercapacitors are considered to be the most-promising energy-

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conversion/storage systems to manage future energy-storage requirements. They are more
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advantageous where long cycle life and the high power density are highly required, such as in

mobile electronic devices, hybrid electric vehicles, memory backup systems, large industrial
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equipment, and military devices [7-8]. According to charge storage mechanism, supercapacitors

are classified into two distinctive parts. First one is the electric double-layer capacitance (EDLC)
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that occurs from pure electrostatic attraction between the charge surface of the electrode and the
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ions, for example the capacitance provided by porous carbon materials [9]. Second one is the

pseudocapacitance that obtained from a Faradic reaction of the electro-active materials with the
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electrolyte ions, such as the capacitance contributed by transition metal oxides [10] or
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electronically conducting polymers [11].

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Conductive polymers such as polyaniline (PANI), polypyrrole (PPy), polythiophene

(PTh) and their derivatives have been widely studied in supercapacitors. Out of these conducting

polymers, PANI is considered one of the most promising candidates due to its high capacitive

characteristics, ease of synthesis and comparatively low cost [12-13]. But PANI restricts

practical applications because of poor cycling life. Nowadays, researcher has resolved those

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problems and provides an innovative route to fabricate PANI-based hybrid composite with

superior performance as electrode materials [14-15].

Graphene (Gr), a two dimensional monolayer of sp2-bonded carbon atoms has received a

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rapidly growing research attention due to its unique electronic and mechanical properties [16-

19]. Gr has drawn extensive research interest in the areas of fabricating electronic and energy

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storage devise, transparent electrodes, sensors, high strength composite materials, anticorrosion

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coatings, and electromagnetic shielding materials [20-21]. By easy chemical processing of

graphite, the graphene-based materials can be simply obtained. Therefore, over the past few

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years, much attention has given on the potential using of graphene-based materials for
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supercapacitor [22-23]. Introduction of various nanoparticles into a graphene-based matrix is an

important study for the investigation of their properties and applications. Among these various
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nanoparticles, silver (Ag) nanoparticles have attracted much more research attention due to their

wide applications and unique properties in biosensing, catalysis, chemical sensing, electronics,
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and photonics [24-27]. It is also well known fact that the incorporation of the Ag nanoparticles
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into the conducting polymer matrices improves the optical, mechanical, thermal, conducing and

electrochemical properties.
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In recent years, the nanocomposites based on Ag nanoparticles decorated on Gr surface

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are reported by various research groups by different synthetic procedure with their different
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applications. Shanmugharaj et al. synthesized graphene-silver nanoparticles hybrids using eco-

friendly microwave radiation and characterized the electrochemical performances [28]. A facile

and green approach is reported by Yuan et al. to synthesized Gr-Ag nanocomposite using sodium

citrate as the reducing agent and checked their surface plasmon resonance property and

antibacterial activity [29]. Wang et al. reported Gr-Ag nanocomposite prepared by one-pot

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reduction of both Ag+ and graphene oxide, and studied their electrochemical oxidation of

methanol in alkaline solution [30]. Gao et al. prepared the paper like Gr-Ag nanocomposite films

synthesized by in-situ reduction of graphene oxide films with Ag+ using ascorbic acid and

investigated their mechanical and electrical properties [31]. Yu et al. prepared Gr-Ag

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nanocomposite by in-situ using ascorbic acid as green reducing agent and checked their

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electrochemical detection of halide [32]. Hsu et al. fabricated the Ag/rGO nanocomposite as a

surface-enhanced Raman scattering (SERS) substrate with high enhancement factor (EF) and

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homogeneity [33]. Li et al. reported a facile strategy to fabricate hair-like nanoarchitectures

made up by ultrafine MnOx nanowires entrapped with ultrafine Ag nanoparticles synthesized by

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in situ reaction between Ag nanowires and KMnO4 and investigated their electrochemical
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behavior [34]. Zhang et al. prepared Gr-Ag nanocomposite in aqueous solution by using tannic

acid and polyphenol as reducing agent and checked their surface enhanced Raman scattering and
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electrochemical properties [35]. The application of GO-Ag nanocomposite in photocurrent

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generation has been demonstrated by Tian et al. [36]. Liu et al. designed and successfully
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fabricated the microsupercapacitors based on the rGO/MnO2/Ag nanowire ternary film [37]. Zhi

et al. developed ordered mesoporous carbon (OMC) based highly conductive and flexible
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electrodes for supercapacitor, employing 3D Gr foam as flexible and conductive scaffold and Ag

nanowires as conductive reinforcing agent [38]. Vanitha et al. prepared Ag/CeO2/rGO ternary
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nanocomposite synthesized by facile hydrothermal method and investigated as electrode

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materials for supercapacitors application [39]. The EMI shielding efficiency and the electrical

conductivity of the polyaniline composite filled with Gr-Ag was investigated by Chen at el. [40].

Sawangphruk et al. prepared Gr-Ag-PANI nanocomposite coated on flexible carbon fiber paper

and investigated their electrochemical properties [41]. Zhang et al. synthesized rGO-Ag

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nanocomposite by one-step photochemical reaction method and checked their catalytic activity

[42]. Therefore we have seen that there are several works done by numerous research groups on

Gr-Ag or GO-Ag and Gr-Ag-PANI nanocomposite, although the synthesis of Ag nanoparticles

by using dodecylbenzenesulfonic acid (DBSA) and silver nitrate (AgNO3) in the presence of

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PANI and Gr is not yet done. In one of our previous study we have synthesized Ag nanoparticles

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decorated PANI/MWCNTs nanocomposite for supercapacitor electrode materials [43]. More

interestingly we want to know how Gr, Ag nanoparticles and PANI effects on the

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electrochemical properties. So, our main motivation of this work to fabricate Ag nanoparticles

decorated PANI-Gr nanocomposites for next generation supercapacitor electrode materials.

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Herein, we report Ag nanoparticles decorated PANI/Gr [Ag-PANI/Gr] nanocomposite

synthesized by a simple and inexpensive in-situ oxidative polymerization technique using

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ammonium persulfate (APS) as an oxidizing agent in presence of DBSA and AgNO3 and

investigated as electrode material for next generation supercapacitor electrode material. The
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electrochemical performances of the electrode material was analyzed by cyclic voltammetry

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(CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS)

analysis with a two-electrode system in two different aqueous electrolytes. The chemical
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interaction, morphological characteristics, electrical properties and thermal stability of the

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nanocomposite, was also investigated.

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2. Experimental section

2.1. Materials used

The monomer, aniline, ammonium persulfate [(NH4)2S2O8], H2SO4, HNO3 and

dimethylformamide (DMF) used in this study was provided by Merck, Darmstadt, Germany.

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Dodecylbenzenesulfonic acid (DBSA) and silver nitrate (AgNO3) were purchased from Sigma-

Aldrich, Bangalore, India. Graphene was supplied from Sinocarbon Materials Technology Co.

Ltd., China. To remove the impurities, the graphene sheets were treated with mixed acid (H2SO4

and HNO3). Cetyltrimethylammonium bromide (CTAB) used in the study was obtained from

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Loba Chemie Pvt. Ltd., Mumbai, India.

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2.2. Synthesis of Ag-PANI/Gr nanocomposite

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The Ag-PANI/Gr nanocomposite was synthesized by in-situ oxidative polymerization

technique. The synthetic procedure of the nanocomposite was the same as our previous study

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[43]. Briefly, 1.24 g of cetyltrimethylammonium bromide (CTAB) and 50 mg of Gr were taken
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in 150 ml of double distilled water and sonicated for 45 minutes at room temperature. 100 ml of

0.01 M AgNO3 solution was taken in a round-bottom flask and stirred for 30 minutes at room
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temperature. Into this solution, 0.01 M DBAS solution was added and stirred for another 15
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minutes. The well-dispersed suspension of Gr solution was then added slowly to the AgNO3
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solution and stirred for 30 minutes. Then the pre-cooled solution of 0.01 M aniline was added to

the above solution and stirred for 8 h at room temperature. Subsequently, 0.01 M APS solution
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was added drop wise to the above solution to initiate the polymerization process. The monomer

and the oxidizing agent ratio were kept as 1:2. Then the entire solution was stirred for another 8
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hours at room temperature and kept at 0–5 oC for overnight to complete the polymerization
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process. Afterward, the greenish black precipitate was filtered and washed with ethanol and

double distilled water for many times to remove the un-reacted monomer. Then, the product was

vacuum-dried at 80 oC for 24 hour to get the Ag-PANI/Gr nanocomposite. The schematic

representation of the synthesis technique of the nanocomposite is illustrated in Fig. 1.

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Fig. 1: Schematic diagram of the nanocomposite synthesis process

2.3. Characterization
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The Fourier transform infrared (FTIR) spectrum was recorded using a NEXUS 870 FT-
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IR (Thermo Nicolet) instrument in the range from 400 to 4000 cm-1. By using a Perkin-Elmer,
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Lambda 750 spectrophotometer, the UV-visible spectra of the nanocomposite was recorded. UV-

visible spectroscopy analysis was executed by dissolving the electrode materials in DMF solvent
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and the spectrum was taken with the 200-800 nm wavelength range. The Raman spectrum was
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recorded with a RAMNOR HG-2S spectrometer (Jobin-Yvon, France) with an argon ion laser
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with 10 mW power. The X-ray diffraction analysis was performed by using PW X-ray

diffractometer with Cu Kα target (λ = 0.15404 nm). The nanocomposite was scanned in the 2θ

range from 10 to 80o at a scanning rate of 2 deg/min having operating voltage and current at 40

kV and 20 mA, respectively. The surface morphology of the nanocomposite was studied by a

field emission scanning electron microscope (Carl Zeiss-SUPRA 40 FESEM) instrument. The

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elemental analysis of the nanocomposite also examined by energy-dispersive X-ray spectroscopy

(EDX) analysis. Transmission electron microscopy (HR-TEM, JEOL 2100) analysis was used to

check the formation of Ag nanoparticles in the PANI coated Gr surfaces. The electrical

conductivity of the nanocomposite was determined by conventional four-probe methods

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(Lakeshore resistivity and Hall measurement setup) with compressed pellet. The pellet was

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prepared by pressing the nanocomposite at 8 MPa pressure and have a diameter of 0.05 mm. The

electrical conductivity (σ) of the nanocomposite was measured by the following equation-

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ρ = πtp/ln 2(V/I)

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= 4.53tp × resistance
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σ/(S/cm) = 1/ρ (1)
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where, ρ is the resistivity in ohm.cm, V is the measured voltage, I is the source current and tp is

the sample thickness. The Keithley 2400 source meter was used to check the current-voltage (I-
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V) behavior of the nanocomposite. A thermogravimertic analyzer (TGA 209F, NETZSCH, Seib,

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Germany) was used to investigate the thermal stability of the nanocomposite. The TGA analysis

was carried out under nitrogen atmosphere at a heating rate of a 10 oC/min.

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2.4. Electrochemical characterization

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The electrochemical characterizations, such as CV, GCD, and EIS analysis, were
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performed using a potentiostatic electrochemical workstation (Biologic SP-150 VMP-3, France)

by the help of two-electrode system, where platinum was used as the counter electrode, which is

also operated as the reference electrode and glassy carbon electrode was used as working

electrode. All the electrochemical performances were carried out in two different aqueous

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electrolytes, 1 M KCl and 1 M Na2SO4 at various scan rates from 5 to 200 mV/s. The specific

capacitance (Cs) of the nanocomposite was determined from cyclic voltammogram by using the

following equation-

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Cs = (2)
(
) 

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where, the numerator of the above equation denotes the total charge under the CV curve, V1 and

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V2 represents the lower and upper voltage limit, v and m is the scan rate and mass (0.1 mg) of the

electrode materials, respectively. Initially, 1 mg of sample was dissolve to 1 mL of 1 % nafion

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solution and sonicated for 15 minutes at room temperature. That solution was then cast onto a
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glassy carbon electrode with 3 mm of diameter. After that this electrode was dried and then

proceeds for electrochemical characterization. This is the procedure for the preparation of
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working electrode.
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The galvanostatic charge/discharge measurements also performed to evaluate the specific

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capacitance of the nanocomposite using the following equation-

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Cs = (3)
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where, i and m denotes the current density in A/g, ∆v signifies the potential range, and t represent
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is the discharge time in seconds.

The energy density and power density values of the nanocomposite were also calculated

from charge/discharge profiles. The energy density of the nanocomposite was evaluated by using

the following equation-

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Energy Density (E) = ½ (CV2) (4)

where, C is the specific capacitance calculated from GCD profile, V is the operating voltage. By

the help of GCD profile, the power density of the nanocomposite was obtained by using the

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following equation [44, 45]-

Power Density (P) = E/t (5)

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where, t is the discharge time obtained from charge-discharge profile.

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3. Result and discussion

3.1. FTIR analysis

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The FTIR spectra of the Ag-PANI/Gr nanocomposite along with pure PANI are shown in
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Fig. 2. Pure PANI shows the characteristic absorption band at 1593, 1477, 1318, 1127, and 820

cm-1, respectively. The band at 1593 cm-1 is assigned for C=C stretching of the quinonoid rings,
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the band at 1477 cm-1 is assigned for stretching of the benzenoid ring, the band at 1318 cm-1 is
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for C–N stretching vibration, the band at 1127 cm-1 is assigned for N=Q=N ring stretching (Q

represents the quinonoid ring), and the band at 820 cm-1 is for out-of-plane C–H bending
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vibration, respectively [46, 47]. The similar types of absorption bands also observed for Ag-

PANI/Gr nanocomposite with some shifting of peaks. The absorption band at 1593 cm-1 shifted
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to 1576 cm-1, the band at 1477 cm-1 shifted to 1500 cm-1, and the band at 1313 cm-1 shifted to
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1303 cm-1, respectively. This shifting of absorption bands is due to the interaction between PANI

and Ag [48]. On the other hand the absorption band at 1127 cm-1 is shifted to 1151 cm-1 for Ag-

PANI/Gr nanocomposite is only because of strong electrostatic interaction between PANI

functionalized Gr and Ag. For both PANI and Ag-PANI/Gr nanocomposite, the board absorption

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band at around 3457 and 3240 cm-1 correspond to the N–H stretching vibration. The band at

2916 and 2862 cm-1 is due to the C–H stretching vibration. The Ag-PANI/Gr nanocomposite

showed absorption band at 1032 cm-1. This band assigned for the stretching vibration of the –

SO3H group, that occurs from the incorporation of DBSA.

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Fig. 2: FTIR spectra of pure PANI and Ag-PANI/Gr nanocomposite

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3.2. UV-Visible spectroscopy analysis

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The electronic property of the Ag-PANI/Gr nanocomposite was studied by UV-visible

spectrum. Fig. 3(a) represents the UV-visible spectra of Ag-PANI/Gr nanocomposite. The

nanocomposite showed three absorption peaks at 272 nm, 380 nm, and 492 nm, respectively. The

absorption peak at around 272 nm can be ascribed to the π–π* transition in the aromatic ring.

Whereas, the absorption peak at around 380 nm is attributed the π–π* transitions in the

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benzonoid unites of the PANI chains. The absorption band at 492 nm is due to the surface

plasmon resonance of the Ag nanoparticles [49]. The existence of such surface palmon resonance

band clearly indicates the presence of Ag nanoparticles in the Ag-PANI/Gr nanocomposite.

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The band gap of the Ag-PANI/Gr nanocomposite was determined from absorption

spectra. According to Tauc relationship the optical band-gap energy was calculated-

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αhν = B(hν – Eg)n (6)

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where, α represents the absorption coefficient, hν signifies the photon energy, B indicates the

proportionality constant, Eg is the optical band gap, and n specifies the specific electronic

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transition liable for light absorption. In this case the n value is ½. By extrapolating the straight
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line portion of the plot of (αhν)2 versus hν to α = 0, the band gap was calculated. The Ag-
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PANI/Gr nanocomposite showed the calculated band gap of 3.20 eV.

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Fig. 3: (a) UV-visible spectra and (b) band gap energy of Ag-PANI/Gr nanocomposite

3.3. Raman spectroscopy analysis

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The Raman spectroscopy is a significant tool for characterizing Gr based materials. The

Raman spectrum of the Ag-PANI-Gr nanocomposite is shown in Fig. 4. The Raman spectrum of

the nanocomposite showed the following main bands at 1150, 1238, 1335, 1377, and 1580 cm-1,

respectively. The band at 1150 cm-1 is associated with the C–H bending of the quinoid ring, the

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band at 1238 cm-1 is assigned for C–H bending of the benzenoid rings, the band at 1335 cm-1 and

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1377 cm-1 is associated with the C–N radical cation and C–N+ polaron, respectively. The

characteristic band at 1580 cm-1 is assigned for the C–C stretching for the benzene rings [50, 51].

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Fig. 4: Raman spectrum of Ag-PANI/Gr nanocomposite

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3.4. XRD analysis

The XRD pattern of the Ag-PANI/Gr nanocomposite is shown in Fig. 5. The crystalline

peaks of Ag nanoparticles exhibited at 2θ = 38.04o, 44.14o, 64.45o, and 77.41o, that corresponded

to the face-centered cubic (fcc) phase of Ag (111), (200), (220), and (311), respectively [51]. The

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sharp diffraction pattern clearly indicated the presence of Ag nanoparticles in the Ag-PANI/Gr

nanocomposite with their crystalline nature. Apart from Ag nanoparticles, the peaks at 2θ =

26.48o is obtained. The occurrence of such peak is due to graphene. It is also observed that the

XRD pattern show a board peak at 2θ values of ~16–23o. The existence of such board peak is

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due to the amorphous behavior of PANI.

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Fig. 5: XRD pattern of Ag-PANI/Gr nanocomposite

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3.5. Surface morphology analysis

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The FESEM analysis was used to investigate the surface morphology of the Ag-PANI/Gr
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nanocomposite. The FESEM image of the nanocomposite is shown in Fig. 6. Fig. 6(a) and (b)

represents the FESEM images of the Ag-PANI/Gr nanocomposite at lower and higher

magnification, respectively. From the FESEM images it is observed that the Gr surfaces are

uniformly coated by PANI and also there is the presence of uniformly distributed Ag

nanoparticles having nanometer in size in the PANI coated Gr surfaces. The average diameter of

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the Ag nanoparticles is around 20–35 nm. Such special type of morphology may enhance the

electrochemical performances of the Ag-PANI/Gr nanocomposite. Gr showed its thin sheet-like

morphology, shown in Fig. 6(c). The energy-dispersive X-ray (EDX) analysis is an analytical

technique utilized for the elemental analysis of a sample. Fig. 6(d) represents the EDX spectra of

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Ag-PANI/Gr nanocomposite. From the EDX spectrum is can be confirmed that the presence of

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Ag nanoparticles in the Ag-PANI/Gr nanocomposite.

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Fig. 6: FESEM images of Ag-PANI/Gr nanocomposite at (a) higher and (b) lower magnification,

(c) Gr, and (D) EDX spectrum of Ag-PANI/Gr nanocomposite

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EDX is more reliable technique for the conformation of the presence of Ag nanoparticles

in the PANI coated Gr surfaces. For this reason we have done the EDX mapping (Ag, N, C) on

the selected area. The FESEM image and the corresponding EDX elements (Ag, N, C) mapping

images are displayed in Fig. 7. Where, Fig. 7(a) represents the FESEM image, Fig. 7(b) signifies

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the silver mapping, Fig. 7(c) specifies the nitrogen mapping, and Fig. 7(d) stands for the carbon

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mapping, respectively. The uniform distribution of silver, nitrogen, and carbon over the selected

area of Ag-PANI/Gr confirms the presence of Ag nanoparticles in the PANI coated Gr surfaces.

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Fig. 7: EDX mapping images of Ag-PANI/Gr nanocomposite: (a) FESEM image, (b) silver

element mapping, (c) nitrogen element mapping, and (d) carbon element mapping

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3.6. TEM analysis

The typical TEM micrographs of the Gr and Ag-PANI/Gr nanocomposite are shown in

Fig. 8. Fig. 8(a) presents the TEM images of Gr and showed its thin sheet-like morphology. Fig.

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8(b) represents the TEM micrograph of Ag-PANI/Gr nanocomposite. It can be seen from the

TEM micrographs that the Gr surfaces are uniformly coated by PANI and also there is the

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presence of randomly distributed of Ag nanoparticles (indicated by pink circles) in the PANI

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coated Gr sheets. It can also be observed that the Ag nanoparticles are about 20–35 nm in size.

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Fig. 8: TEM Micrographs of (a) Gr and (b) Ag-PANI/Gr nanocomposite

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Fig. 9 presented the selected area electron diffraction (SAED) patterns of the Gr and Ag-
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PANI/Gr nanocomposite. It can be observed that the Gr achieved perfect six-membered ring

pattern signifying the crystalline nature of the Gr sheets, shown in Fig. 9(a). Fig. 9(b) represents

the SAED pattern of Ag-PANI/Gr nanocomposite and obtained the ring-like diffraction pattern

that indicates the Ag nanoparticles are crystalline in nature. The occurrence of such rings are due

to the reflections from (111), (200), (220), and (311) lattice planes of fcc Ag, respectively.

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Fig. 9: SAED patterns of (a) Gr and (b) Ag-PANI/Gr nanocomposite

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3.7. Electrochemical characterization

The electrochemical behavior of the Ag-PANI/Gr nanocomposite is analyzed through

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CV, GCD, and EIS analysis by the help of two-electrode system. Both 1 M KCl and 1 M Na2SO4
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solution were used as electrolyte for all the electrochemical performances. The electrochemical
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behavior of an electrode material not only depends on the nature, conductivity and porosity of

the electrode materials but also on the nature of the electrolytes. The selection of electrolyte
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depends on various points such as capacitance, resistance, manufacturing cost and also on the

stable potential window [52]. In terms of cost and safety point of view, the aqueous electrolytes
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are better for electrochemical characterization compared to organic electrolyte. It is well known
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that the aqueous electrolytes are environmentally friendly. It is also well known fact the cycling

performance of a supercapacitor is better in aqueous electrolytes in comparison with organic

electrolytes.

3.7.1. Cyclic voltammetry

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The CV curves of the Ag-PANI/Gr nanocomposite at different electrolytes are shown in

Fig. 10. The nanocomposite was examined within 0 – 0.5 V potential window at a different scan

rate of 5, 10, 20, 50, 100, and 200 mV/s, respectively. In both the electrolytes relatively

rectangular shape in CV curve was obtained for the Ag-PANI/Gr nanocomposite that indicates

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the superior supercapacitor performance. From the CV curve it can be seen that the redox peak is

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absent though redox active materials are present. This behavior indicates that the

charging/discharging takes place at a pseudo-constant rate over the whole volumetric cycles. By

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the help of Equation 2 we have calculated the specific capacitance of the Ag-PANI/Gr

nanocomposite. The nanocomposite showed highest specific capacitance value of 591 F/g at 5

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mV/s scan rate in 1 M KCl electrolyte. Whereas, in 1 M Na2SO4 electrolyte the nanocomposite
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achieved the specific capacitance value of 477 F/g at the same scan rate. The improvement of

such specific capacitance value of the Ag-PANI/Gr nanocomposite is due to the following
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causes: (i) the presence of Ag nanoparticles having 20–35 nm size in the nanocomposite
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increases the specific capacitance; (ii) the presence of high surface area Gr in the Ag-PANI/Gr
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nanocomposite enhances the specific capacitance; (iii) there is the good interaction between Ag

nanoparticles with the PANI chains and also with the Gr; and (iv) the uniform coating of PANI
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on Gr surfaces and also there is the presence of uniformly distributed Ag nanoparticles in the

PANI coated Gr surfaces makes a unique morphology which can play a important role for the
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enhancement of the specific capacitance of the Ag-PANI/Gr nanocomposite. Fig. 11 represents

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the plot of specific capacitance vs. scan rate. It is observed that with increasing in the scan rates

the specific capacitance values decreases. This behavior indicating that the charge storage

mechanism was only because of diffusion electrochemistry. At higher scan rate, the electrolytes

(i.e., K+ or Na+ and H+) can only arrive at the outer surface of the electrodes that’s why the

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specific capacitance value decreases. Whereas, at lower scan rate, the electrolytes have sufficient

time to get into deep pores of the electrodes and increases the specific capacitance value.

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Fig. 10: Cyclic voltammogram at different scan rate of Ag-PANI/Gr nanocomposite (a) in 1 M
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KCl solution, and (b) in 1 M K2SO4 solution

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Fig. 11: Plot of specific capacitance vs. scan rate

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3.7.2. Galvanostatic charge–discharge behavior

The specific capacitance of Ag-PANI/Gr nanocomposite was also investigated by the

help of galvanostatic charge–discharge (GCD) tests in two different electrolytes, plots shown in

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Fig. 12. Fig. 12(a) & (b) represents the GCD plots of the Ag-PANI/Gr nanocomposite at 1 M

KCl and at 1 M Na2SO4 electrolyte, respectively. The GCD behavior of the Ag-PANI/Gr

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nanocomposite was studied at different current densities such as, 0.5, 1, 1.5, 2, and 3 A/g within

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the voltage range in between 0 to 0.5 V. The equilateral triangle shape in charge–discharge

curves was obtained from GCD profile, which indicates the potential of charge–discharge

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displays a linear response to time. This performance specifies an excellent reversibility during
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the charging and discharging processes, hence exhibiting superior capacitive behavior. It can be

clearly seen from the GCD curve that the time duration of charging and discharging increases
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with decrease in the current density, that advantages to better specific capacitance by lowering

the resistivity of the electrode. By using Equation 3, we have calculated the specific capacitance
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of the Ag-PANI/Gr nanocomposite. The Ag-PANI/Gr nanocomposite achieved the better

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specific capacitance value of 583 F/g at a 0.5 A/g current density in 1 M KCl electrolyte. But,

when 1 M K2SO4 used as electrolyte the specific capacitance reduced to 467 F/g at the same
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current density. The main reason behind highest specific capacitance in 1 M KCl electrolyte is
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that the hydrated ionic radius of K+ is 3.31 Å, which is smaller than the hydrated ionic radius of
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Na+ that is 3.58 Å. Due to smaller ionic radius, K+ ions are easier and faster accessibility into the

inner active surface of the electrode material as compared to Na+ [53]. Fig. 13 represents the plot

of specific capacitance at various current densities. It is observed that at higher current densities

or faster charging, specific capacitance values decreases that demonstrating the energy storage

mechanism are only because of electrochemical diffusion.

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The specific capacitance value which we have reported for the Ag-PANI/Gr

nanocomposite is much higher as compared to the related literature values. The comparison of

specific capacitance of Ag-PANI/Gr nanocomposite with those of previous related works in

summarized in Table 1.

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Table 1: Comparison of specific capacitance of Ag-PANI/Gr nanocomposite with those of

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previous related works

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Electrode Measurement Electrolyte Specific capacitance References
materials type (F/g)
Ag-PANI 3-electrode 1 M KCl 425 F/g at 5 mV/s scan 43

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rate
Ag-RGO 3-electrode 2 mol/L KNO3 220 F/g at 10 mV/s scan 54
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rate
Ag-PANI 3-electrode 1 M H2SO4 512 F/g at 5 mV/s scan 55
arte
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G-PANI 2-electrode 2 M H2SO4 400 F/g at 5 mV/s scan 56

rate
3D Gr-PANI 3-electrode 1 M H2SO4 346 F/g at 4 A/g current 57
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density
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Gr-PANI 3-electrode 1 M H2SO4 489 F/g at 400 mA/g 58

current density
Gr-PANI 3-electrode 1 M H2SO4 257 F/g at 0.1 A/g 59
current density
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Gr-PANI-F 3-electrode 2 M H2SO4 526 F/g at 0.2 A/g 60

current density
Gr-PANI 3-electrode 2 M H2SO4 480 F/g at 0.1 A/g 61
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nanofiber current density

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PANI-g-rGO 3-electrode 1 M H2SO4 250 F/g at 100 scan rate 62

Gr-PANI 3-electrode 1 M H2SO4 233 F/g at 2 mV/s scan 63
rate
Gr-PANI 2-electrode 1 M H2SO4 210 F/g at 0.3 A/g 64
nanofiber current density
1 M KCl 591 F/g at 5 mVs/scan Present
Ag-PANI/Gr 2-electrode rate study
1 M Na2SO4 477 F/g at 5 mV/s scan
rate

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Fig. 12: Galvanostatic charge–discharge plot at different current densities of Ag-PANI/Gr

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nanocomposite at (a) 1 M KCl and (b) 1 M Na2SO4 electrolyte
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Fig. 13: Plot of specific capacitance vs. current density

The energy density and power density are the two very important parameters of

supercapacitors for applications in the energy storage systems. But the supercapacitor electrode

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materials have the disadvantage of lower energy density. Our as synthesized electrode material

reached the reasonable energy as well as power densities. By the help of Equation 4 we have

calculated the energy density of the Ag-PANI/Gr nanocomposite. The nanocomposite achieved

the better energy density of 20.24 Wh/kg at a 0.5 A/g current density in 1 M KCl electrolyte.

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While the nanocomposite showed the energy density of 16.21 Wh/kg at the same current density

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in 1 M Na2SO4 electrolyte. Again by using the Equation 5, we have computed the power density

of the nanocomposite. The Ag-PANI/Gr nanocomposite showed the power density of 749.30 and

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668.34 W/kg at a current density of 3 A/g in 1 M KCl and in 1 M Na2SO4 electrolyte,

respectively. Fig. 14 shows the plot of energy density vs. power density also known as “Ragone

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Plot”. It can be noticed that at various energy densities, the corresponding power density values
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are much greater than those of conventional supercapacitors.
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Fig. 14: Ragone plot (energy density vs. power density) of the Ag-PANI/Gr nanocomposite

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The electrochemical stability of the as prepared Ag-PANI/Gr nanocomposite was

calculated using GCD test over 1500 charge–discharge cycles at a current density of 0.5 A/g.

The cyclic stability test was carried out in both the electrolyte. Fig. 15 represents the plot of

specific capacitance vs. number of cycles. It can be observed that the Ag-PANI/Gr

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nanocomposite retained their 96% specific capacitance after 1500 consecutive charge–discharge

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cycles in 1 M KCl electrolyte. In case of 1 M K2SO4 electrolyte, the nanocomposite showed the

specific capacitance retention of 93% after the same charge–discharge cycles. The improved

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cyclic stability of the Ag-PANI/Gr nanocomposite in both the electrolyte is due to the presence

of Ag nanoparticles and also the Gr.

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Fig. 15: Plot of specific capacitance vs. cycle number of Ag-PANI/Gr nanocomposite at different

electrolyte

3.7.3. Electrochemical impedance spectroscopy

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The dielectric properties of any materials as a function of frequency were investigated by

the help of EIS analysis. Nyquist plot is the most usually plots for the analysis of the EIS data.

The Nyquist plots are naturally interpreted by fitting the experimental impedance spectra to an

appropriate equivalent electrical circuit. Nyquist plots are the plots of real component (Z‫ )׳‬of the

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impedance vs. the imaginary component (–Z‫ )״‬of the impedance. Fig. 16 shows the Nyquist plots

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of the Ag-PANI/Gr nanocomposite at two different electrolytes. In the plots, the area at higher

frequency represents the electrolyte properties and the area at the middle frequency is associated

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with the electrode–electrolyte interface. The appropriate equivalent circuit used for fitting the

Nyquist plots is shown in Fig. 17, and the fitting data are summarized in Table 2. In the circuit,

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the term Rs, Rct, CPE, n, and Wd indicates the solution resistance, charge–transfer resistance,
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constant–phase element, frequency factor, and Warburg coefficient, respectively. The solution

resistance of 1.225 Ω and 1.332 Ω is obtained for the Ag-PANI/Gr nanocomposite in 1 M KCl
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and 1 M Na2SO4 electrolyte, respectively. The lower solution resistance value in 1 M KCl
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electrolyte specifies the higher conductively and also the better specific capacitance. For any
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supercapacitor electrode materials the most important parameter is the frequency factor (n). That

provides the information about ideality of a material towards supercapacitive behavior. When, n
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= 1 indicates the ideal behavior, n = 0.5 specifies the low supercapacitive behavior and n = 0.5–1

signifies the moderate supercapacitive behavior. Our as synthesized nanocomposite showed the
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moderate supercapacitor behavior. The highest n value of 0.96 was obtained when in 1 M KCl
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was used as electrolyte.

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Fig. 16: Nyquist plot of Ag-PANI/Gr nanocomposite in (a) 1 M KCl and (b) in 1 M Na2SO4

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solution
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Fig. 17: Equivalent circuit used for fitting the Nyquist plots
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Table 2: Fitting data of equivalent circuit elements obtained by simulation of impedance spectra
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Sample Rs (Ω) Rct (Ω) W (S – s0.5) × 10-2 CPE (S – sn) × 10-3 n

Ag-PANI/Gr [1M KCl] 1.225 32.44 0.11 0.088 0.96
Ag-PANI/Gr [1M Na2SO4] 1.332 35.30 0.15 0.038 0.91

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3.8. Electrical conductively measurements

The electrical conductivity of the Ag-PANI/Gr nanocomposite was carried out by four–

probe measurements at room temperature. The nanocomposite achieved the highest electrical

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conductivity of 5.17 S/cm at room temperature. The obtained electrical conductivity value is

much higher than our previous reported value [43]. The presence of Ag nanoparticles in the Ag-

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PANI/Gr nanocomposite enhances the electrical conductivity. Apart from Ag nanoparticles, the

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presence of high surface area Gr in the nanocomposite also take part for the increment of the

electrical conductivity.

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3.9. Current (I) – voltage (V) characteristic
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The I–V characteristic of the Ag-PANI/Gr nanocomposite was determined within the
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voltage range from –10 to 10 V at room temperature. The I–V characteristic of the

nanocomposite is shown in Fig. 18. It can be seen that the current is raises with raising the
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applied voltage in a nonlinear manner. This nonlinearity of the I–V curve simply indicates the
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semiconducting behavior of the nanocomposite.

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Fig. 18: I – V characteristic of the Ag-PANI/Gr nanocomposite

3.10. Thermogravimertic analysis

The effect of Gr and Ag nanoparticles on the thermal stability of the nanocomposite was

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investigated by TGA analysis. The TGA thermogram of pure PANI as well as Ag-PANI/Gr

nanocomposite was shown in Fig. 19. Both the electrode materials showed the initial weight loss

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is due the presence of volatile impurities. We have calculated the percentage of weight loss at

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different temperatures and summarized in Table 3. It is observed that at 100 oC, the Ag-PANI/Gr

shows the weight loss of only 3.23% and the PANI shows the weight loss of 10.18%. As the

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temperature increases the thermal stability of the Ag-PANI/Gr nanocomposite also increases.
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The enhancement of thermal stability of the nanocomposite is mainly because of the presence of

Ag nanoparticles and also the presence of Gr in the nanocomposite. The typical morphology
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where Gr surfaces are uniformly coated by PANI and also there is the presence of uniformly
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distribution of Ag nanoparticles helps for the increment of the thermal stability of the Ag-

PANI/Gr nanocomposite. It can also be seen that at 350 oC, the nanocomposite loss their 25.41%
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weight whereas PANI shows the weight loss of 33.71% at that temperature. One important
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phenomenon also observed that after 400 oC the nanocomposite decreased their thermal stability.

The reason behind such behavior is that after 400 oC the bonded interaction between PANI and
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Ag is not stable after that temperature. For this reason sudden decrease in the thermal stability
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was observed for Ag-PANI/Gr nanocomposite.

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Fig. 19: TGA thermograms of pure PANI and Ag-PANI/Gr nanocomposite
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Table 3: Thermal stability data for pure PANI and Ag-PANI/Gr nanocomposite extracted from
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TGA thermograms
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Sample Weight loss at temperature (%)

o
100 C 200 oC 350 oC
PANI 10.18 16.05 33.71
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Ag-PANI/Gr 3.23 4.51 25.41

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4. Conclusions
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The nanocomposite based on Ag nanoparticles decorated PANI/Gr was synthesized

successfully by simple and inexpensive in-situ polymerization techniques. Spectral analysis

(FTIR, UV, and Ramam) confirmed the interaction of Ag nanoparticles with both Gr and also

PANI. The formation of Ag nanoparticles having nanometer in size in the PANI coated Gr

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surfaces were confirmed by morphological analysis: FESEM and TEM. The presence of Ag

nanoparticles and also the special type of morphology improved the electrochemical

performances of the Ag-PANI/Gr nanocomposite. The nanocomposite showed the highest

specific capacitance value of 591 F/g at a 5 mV/s scan rate in 1 M KCl electrolyte. The

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nanocomposite attend better energy density of 20.24 Wh/kg at 0.5 A/g current density and higher

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power density of 749.30 W/kg at 3 A/g current density. The nanocomposite also retained their

96% specific capacitance after 1500 charge–discharge cycles. The superior electrochemical

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performances are obtained in KCl electrolyte as compared to Na2SO4 electrolyte. The presence

of Ag nanoparticles improved the electrical conductivity of the nanocomposite and which is 5.17

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S/cm at room temperature. The semiconducting nature of the nanocomposite was confirmed by
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o
I–V characteristic. Superior thermal stability (up to 400 C) also exhibited for the

nanocomposite. Based on the above mentioned superior properties the nanocomposite can be
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used for the electrode materials for supercapacitors.

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Acknowledgement
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The first author thank to Council of Scientific and Industrial Research (CSIR),
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New Delhi, India for providing the fellowship. We gratefully acknowledge Sandipta Roy,

CRNTS, IIT Bombay for Raman Analysis. We are also thankful to IIT Kharagpur for
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instrumental facilities.
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Highlights:
1. Ag nanoparticles decorated PANI/Gr nanocomposite has been synthesized.
2. Ag nanoparticles decorated on the PANI coated Gr surfaces.
3. The typical morphology and Ag nanoparticles enhances the electrochemical performances

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4. 1 M KCl electrolyte showed better electrochemical performances than 1 M K2SO4 electrolyte
5. The nanocomposite attend highest electrical conductivity and better thermal stability

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